nano and molecular electronics handbook, 2007, p.931

NANO
and
MOLECULAR
ELECTRONICS
Handbook
Nano- and Microscience, Engineering,
Technology, and Medicine Series
Series Editor
Sergey Edward Lyshevski
Titles in the Series
Logic Design of NanoICS
Svetlana Yanushkevich
MEMS and NEMS:
Systems, Devices, and Structures
Sergey Edward Lyshevski
Microelectrofluidic Systems: Modeling and Simulation
Tianhao Zhang, Krishnendu Chakrabarty,
and Richard B. Fair
Micro Mechatronics: Modeling, Analysis, and Design
with MATLAB
®
Victor Giurgiutiu and Sergey Edward Lyshevski
Microdrop Generation
Eric R. Lee
Nano- and Micro-Electromechanical Systems: Fundamentals
of Nano- and Microengineering
Sergey Edward Lyshevski
Nano and Molecular Electronics Handbook
Sergey Edward Lyshevski
Nanoelectromechanics in Engineering and Biology

Michael Pycraft Hughes
CRC Press
Taylor & Francis Group
6000 Broken Sound Parkway NW, Suite 300
Boca Raton, FL 33487-2742
© 2007 by Taylor & Francis Group, LLC
CRC Press is an imprint of Taylor & Francis Group, an Informa business
No claim to original U.S. Government works
Printed in the United States of America on acid-free paper
10 9 8 7 6 5 4 3 2 1
International Standard Book Number-10: 0-8493-8528-8 (Hardcover)
International Standard Book Number-13: 978-0-8493-8528-5 (Hardcover)
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Library of Congress Cataloging-in-Publication Data
Nano and molecular electronics handbook / editor, Sergey E. Lyshevski.
p. cm. (Nano- and microscience, engineering, technology, and
medicine series)

Includes bibliographical references and index.
ISBN-13: 978-0-8493-8528-5 (alk. paper)
ISBN-10: 0-8493-8528-8 (alk. paper)
1. Molecular electronics Handbooks, manuals, etc. I. Lyshevski, Sergey Edward. II. Title. III. Series.
TK7874.8.N358 2007
621.381 dc22 2006101011
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The Editor
Sergey EdwardLyshevski was born in Kiev, Ukraine. He received his M.S. (1980) and Ph.D. (1987) degrees
from Kiev Polytechnic Institute, both in electrical engineering. From 1980 to 1993, Dr. Lyshevski held
faculty positions at the Department of Electrical Engineering at Kiev PolytechnicInstitute and the Academy
of Sciences of Ukraine. From 1989 to 1993, he was the Microelectronic and Electromechanical Systems
Division Head at the Academy of Sciences of Ukraine. From 1993 to 2002, he was with Purdue School of
Engineering as an associate professor of electrical and computer engineering. In 2002, Dr. Lyshevski joined

Rochester Institute of Technology as a professor of electrical engineering. Dr. Lyshevski serves as a Full
Professor Faculty Fellow at the U.S. Air Force Research Laboratories and Naval Warfare Centers. He is the
author of ten books (including Logic Design of NanoICs, coauthored with S. Yanushkevich and V. Shmerko,
CRCPress, 2005; Nano- and Microelectromechanical Systems: Fundamentals of Micro-andNanoengineering,
CRC Press, 2004; MEMS and NEMS: Systems, Devices, and Structures, CRC Press, 2002) and is the author or
coauthor of more than 300 journal articles, handbook chapters, and regular conference papers. His current
research activities are focused on molecular electronics, molecular processing platforms, nanoengineering,
cognitive systems, novel organizations/architectures, new nanoelectronic devices, reconfigurable super-
high-performance computing, and systems informatics. Dr. Lyshevski has made significant contributions
in the synthesis, design, application, verification, and implementation of advanced aerospace, electronic,
electromechanical, and naval systems. He has made more than 30 invited presentations (nationally and
internationally) and serves as an editor of the Taylor & Francis book series Nano- and Microscience,
Engineering, Technology, and Medicine.
vii

Contributors
Rajeev Ahuja
Condensed Matter Theory
Group
Department of Physics
Uppsala University
Uppsala, Sweden
Richard Akis
Center for Solid State
Engineering Research
Arizona State University
Tempe, Arizona, USA
Andrea Alessandrini
CNR-INFM-S3
NanoStructures and

BioSystems at Surfaces
Modena, Italy
Supriyo Bandyopadhyay
Department of Electrical and
Computer Engineering
Virginia Commonwealth
University
Richmond, Virginia, USA
Valeriu Beiu
United Arab Emirates
University
Al-Ain, United Arab Emirates
Robert R. Birge
Department of Chemistry
University of Connecticut
Storrs, Connecticut, USA
A.M. Bratkovsky
Hewlett-Packard Laboratories
Palo Alto, California, USA
J.A. Brown
Department of Physics
University of Alberta
Edmonton, Canada
K. Burke
Department of Chemistry
University of California
Irvine, California, USA
Horacio F. Cantiello
Massachusetts General Hospital
and

Harvard Medical School
Charlestown, Massachusetts,
USA
Aldo Di Carlo
Universit
`
adiRoma
Tor Vergata
Roma, Italy
G.F. Cerofolini
STMicroelectronics
Post-Silicon Technology
Milan, Italy
J. Cuevas
Grupo de F
´
ısica No Lineal
Departamento de F
´
ısica
Aplicada I
ETSI Inform Universidad
de Sevilla
Sevilla, Spain
Shamik Das
Nanosystems Group
The MITRE Corporation
McLean, Virginia, USA
John M. Dixon
Massachusetts General Hospital

and
Harvard Medical School
Charlestown, Massachusetts,
USA
J. Dorignac
College of Engineering
Boston University
Boston, Massachusetts, USA
Rodney Douglas
Institute of Neuroinformatics
Zurich, Switzerland
J.C. Eilbeck
Department of Mathematics
Heriot-Watt University
Riccarton, Edinburgh, UK
James C. Ellenbogen
Nanosystems Group
The MITRE Corporation
McLean, Virginia, USA
Christoph Erlen
Technische Universit
¨
at
M
¨
unchen
M
¨
unchen, Germany
F. E ve r s

Institut f
˙
ur Theorie der
Kondensierten Materie
Universit
¨
at Karlsruhe
Karlsruhe, Germany
ix
Paolo Facci
CNR-INFM-S3
NanoStructures and
BioSystems at Surfaces
Modena, Italy
DavidK.Ferry
Center for Solid State
Engineering Research
Arizona State University
Tempe, Arizona, USA
Danko D. Georgiev
Laboratory of Molecular
Pharmacology
Faculty of Pharmaceutical
Sciences
Kanazawa University Graduate
School of Natural Science
and Technology
Kakuma-machi Kanazawa
Ishikawa, Japan
James F. Glazebrook

Department of Mathematics
and Computer Science
Eastern Illinois University
Charleston, Illinois, USA
Anton Grigoriev
Condensed Matter Theory
Group
Department of Physics
Uppsala University
Uppsala, Sweden
Rikizo Hatakeyama
Department of Electronic
Engineering
Tohoku University
Sendai/Japan
Thorsten Hansen
Department of Chemistry and
International Institute for
Nanotechnology
Northwestern University
Argonne, Evanston,
Illinois, USA
Jason R. Hillebrecht
Department of Molecular and
Cell Biology
University of Connecticut
Storrs, Connecticut, USA
Walid Ibrahim
United Arab Emirates
University

Al-Ain, United Arab Emirates
Giacomo Indiveri
Institute of Neuroinformatics
Zurich, Switzerland
Dustin K. James
Department of Chemistry
Rice University
Houston, Texas, USA
Bhargava Kanchibotla
Department of Electrical and
Computer Engineering
Virginia Commonwealth
University
Richmond, Virginia, USA
Jeremy F. Koscielecki
Department of Chemistry
University of Connecticut
Storrs, Connecticut, USA
Mark P. Krebs
Department of Ophthalmology
College of Medicine
University of Florida
Gainesville, Florida, USA
Craig S. Lent
Department of Electrical
Engineering
University of Notre Dame
Notre Dame, Indiana, USA
Takhee Lee
Department of Materials

Science and Engineering
Gwangju Institute of Science
and Technology
Gwangju, Korea
Paolo Lugli
Technische Universit
¨
at M
¨
unchen
M
¨
unchen, Germany
Sergey Edward Lyshevski
Department of Electrical
Engineering
Rochester Institute of
Technology
Rochester, New York, USA
Lyuba Malysheva
Bogolyubov Institute for
Theoretical Physics
Kiev, Ukraine
Thomas Marsh
University of St. Thomas
St. Paul, Minnesota, USA
Duane L. Marcy
Department of Electrical
Engineering and Computer
Science

Syracuse University
Syracuse, New York, USA
Robert M. Metzger
Laboratory for Molecular
Electronics
Department of Chemistry
University of Alabama
Tuscaloosa, Alabama, USA
M. Meyyappan
Center for Nanotechnology
NASA Ames Research Center
Moffett Field, California, USA
Lev G. Mourokh
Physics Department
Queens College of the City
University of New York
Flushing, New York, USA
x
Vladimiro Mujica
Department of Chemistry and
International Institute for
Nanotechnology
Northwestern University
Evanston, Illinois, USA
and
Argonne National Laboratory
Center for Nanoscale
Materials
Argonne, Illinois, USA
Alexander Onipko

IFM
Linkping University
Linkping, Sweden
Alexei O. Orlov
Department of Electrical
Engineering
University of Notre Dame
Notre Dame, Indiana, USA
F. Palmero
Grupo de F
´
ısica No Lineal
Departamento de F
´
ısica
ETSI Inform Universidad
de Sevilla
Sevilla, Spain
Alessandro Pecchia
Universit
`
adiRoma
Tor Vergata
Roma, Italy
Carl A. Picconatto
Nanosystems Group
The MITRE Corporation
McLean, Virginia, USA
Sandipan Pramanik
Department of Electrical and

Computer Engineering
Virginia Commonwealth
University
Richmond, Virginia, USA
Avner Priel
Department of Physics
University of Alberta
Edmonton, Alberta, Canada
Mark A. Ratner
Department of Chemistry and
International Institute for
Nanotechnology
Northwestern University
Evanston, Illinois, USA
Mark A. Reed
Departments of Electrical
Engineering, Applied
Physics, and Physics
Yale University
New Haven, Connecticut, USA
R.A. R
¨
omer
Department of Physics and
Centre for Scientific
Computing
University of Warwick
Coventry, UK
F.R. Romero
Grupo de F

´
ısica No Lineal
Departamento de FAMN
Facultad de F
´
ısica
Universidad de Sevilla
Sevilla, Spain
Garrett S. Rose
Department of Electrical
and Computer Engineering
Polytechnic University
Brooklyn, New York, USA
Anatoly Yu. Smirnov
Quantum Cat Analytics Inc.
Brooklyn, New York, USA
Gregory L. Snider
Department of Electrical
Engineering
University of Notre Dame
Notre Dame, Indiana, USA
Gil Speyer
Center for Solid State
Engineering Research
Arizona State University
Tempe, Arizona, USA
Jeffrey A. Stuart
Department of Chemistry
University of Connecticut
Storrs, Connecticut, USA

William Tetley
Department of Electrical
Engineering and Computer
Science
Syracuse University
Syracuse, New York, USA
James M. Tour
Department of Chemistry
Rice University
Houston, Texas, USA
Jack A. Tuszynski
Department of Physics
University of Alberta
Edmonton, Alberta, Canada
James Vesenka
University of New England
Biddeford, Maine, USA
Wenyong Wang
Semiconductor Electronics
Division
National Institute of Standards
and Technology
Gaithersburg, Maryland, USA
Bangwei Xi
Department of Chemistry
Syracuse University
Syracuse, New York, USA
Bin Yu
Center for Nanotechnology
NASA Ames Research Center

Moffett Field, California, USA
Matthew M. Ziegler
IBM T. J. Watson Research
Center
Yorktown Heights, New York,
USA
xi

Contents
Section I Molecular and Nano Electronics: Device- and
System-Level
1 Electrical Characterization of Self-Assembled Monolayers
Wenyong Wang, Takhee Lee, and Mark A. Reed
1-1
2 Molecular Electronic Computing Architectures
James M. Tour and Dustin K. James
2-1
3 Unimolecular Electronics: Results and Prospects
Robert M. Metzger
3-1
4 Carbon Derivatives
Rikizo Hatakeyama
4-1
5 System-Level Design and Simulation of Nanomemories and Nanoprocessors
Shamik Das, Carl A. Picconatto, Garrett S. Rose, Matthew M. Ziegler,
and James C. Ellenbogen
5-1
6 Three-Dimensional Molecular Electronics and Integrated Circuits for Signal
and Information Processing Platforms
Sergey Edward Lyshevski

6-1
Section II Nanoscaled Electronics
7 Inorganic Nanowires in Electronics
Bin Yu and M. Meyyappan
7-1
8 Quantum Dots in Nanoelectronic Devices
Gregory L. Snider, Alexei O. Orlov, and Craig S. Lent
8-1
9 Self Assembly of Nanostructures Using Nanoporous Alumina Templates
Bhargava Kanchibotla, Sandipan Pramanik, and Supriyo Bandyopadhyay
9-1
xiii
10 Neuromorphic Networks of Spiking Neurons
Giacomo Indiveri and Rodney Douglas
10-1
11 Allowing Electronics to Face the TSI Era—Molecular Electronics and Beyond
G. F. Cerofolini
11-1
12
On Computing Nano-Architectures Using Unreliable Nanodevices
Valeriu Beiu and Walid Ibrahim
12-1
Section III Biomolecular Electronics and Processing
13 Properties of “G-Wire” DNA
Thomas Marsh and James Vesenka
13-1
14 Metalloprotein Electronics
Andrea Alessandrini and Paolo Facci
14-1
15 Localization and Transport of Charge by Nonlinearity and Spatial Discreteness

in Biomolecules and Semiconductor Nanorings. Aharonov–Bohm Effect
for Neutral Excitons
F. Palmero, J. Cuevas, F.R. Romero, J.C. Eilbeck, R.A. R¨omer, and J. Dorignac
15-1
16 Protein-Based Optical Memories
Jeffrey A. Stuart, Robert R. Birge, Mark P. Krebs, Bangwei Xi, William Tetley,
Duane L. Marcy, Jeremy F. Koscielecki, and Jason R. Hillebrecht
16-1
17 Subneuronal Processing of Information by Solitary Waves
and Stochastic Processes
Danko D. Georgiev and James F. Glazebrook
17-1
18 Electronic and Ionic Conductivities of Microtubules and Actin Filaments,
Their Consequences for Cell Signaling and Applications to Bioelectronics
Jack A. Tuszynski, Avner Priel, J.A. Brown, Horacio F. Cantiello,
and John M. Dixon
18-1
Section IV Molecular and Nano Electronics: Device-Level
Modeling and Simulation
19 Simulation Tools in Molecular Electronics
Christoph Erlen, Paolo Lugli, Alessandro Pecchia, and Aldo Di Carlo
19-1
20 Theory of Current Rectification, Switching, and the Role of Defects
in Molecular Electronic Devices
A.M. Bratkovsky
20-1
21 Complexities of the Molecular Conductance Problem
Gil Speyer, Richard Akis, and David K. Ferry
21-1
xiv

22 Nanoelectromechanical Oscillator as an Open Quantum System
Lev G. Mourokh and Anatoly Yu. Smirnov
22-1
23 Coherent Electron Transport in Molecular Contacts: A Case
of Tractable Modeling
Alexander Onipko and Lyuba Malysheva
23-1
24 Pride, Prejudice, and Penury of ab initio Transport Calculations
for Single Molecules
F. Evers and K. Burke
24-1
25
Molecular Electronics Devices
Anton Grigoriev and Rajeev Ahuja
25-1
26 An Electronic Cotunneling Model of STM-Induced Unimolecular
Surface Reactions
Vladimiro Mujica, Thorsten Hansen, and Mark A. Ratner
26-1
Index I-1
xv

Preface
It was a great pleasure to edit this handbook, which consists of outstanding chapters written by acclaimed
experts in their field. The overall objective was to provide coherent coverage of a broad spectrum of issues
in molecular and nanoelectronics (e.g., covering fundamentals, reporting recent innovations, devising novel
solutions, reporting possible technologies, foreseeing far-reaching developments, envisioning new paradigms,
etc.). Molecular and nanoelectronics is a revolutionary theory- and technology-in-progress paradigm. The
handbook’s chapters document sound fundamentals and feasible technologies, ensuring a balanced coverage
and practicality. There should be no end to molecular electronics and molecular processing platforms (

M
PPs),
which ensure superior overall performance and functionality that cannot be achieved by any envisioned
microelectronics innovations.
Due to inadequate commitments to high-risk/extremely-high-pay-off developments, limited knowledge,
and the abrupt nature of fundamental discoveries and enabling technologies, it is difficult to accurately predict
when various discoveries will mature in the commercial product arena. For more than six decades, large-scale
focused efforts have concentrated on solid-state microelectronics. A matured $150-billion microelectronics
industry has profoundly contributed to technological progress and societal welfare. However, further progress
and envisioned microelectronics evolutions encounter significant fundamental and technological challenges
and limits. Those limits may not be overcome. In attempts to find new solutions and define novel inroads,
innovative paradigms and technologies have been devised and examined. Molecular and nanoelectronics have
emerged as one of the most promising solutions.
The difference between molecular- (nano) and micro-electronics is not the size (dimensionality), but the
profoundly different device- and system-level solutions, the device physics, and the phenomena, fabrication,
and topologies/organizations/architectures. For example, a field-effect transistor with an insulator thickness
less than 1 nm and a channel length less than 20 nm cannot be declared a nanoelectronic device even though
it has the subnanometer insulator thickness and may utilize a carbon nanotube (with a diameter under
1 nm) to form a channel. Three-dimensional topology molecular and nanoelectronic devices, engineered
from atomic aggregates and synthesized utilizing bottom-up fabrication, exhibit quantum phenomena and
electrochemomechanical effects that should be uniquely utilized. The topology, organization, and architecture
of three-dimensional molecular integrated circuits (
M
ICs) and
M
PPs are entirely different compared with
conventional two-dimensional ICs.
Questions regarding the feasibility of molecular electronics and
M
PPs arise. No conclusive evidence exists

of the overall feasibility of solid
M
ICs and there was no analog for solid-state microelectronics and ICs existed
in the past. In contrast, an enormous variety of biomolecular processing platforms are visible in nature. These
platforms provide one with undeniable evidence of feasibility, soundness, and unprecedented supremacy of
a molecular paradigm. Though there have been attempts to utilize and prototype biocentered electronics,
processing, and memories, these efforts have faced—and still face—enormous fundamental, experimental,
and technological challenges. Superior organizations and architectures of
M
ICs and
M
PPs can be devised
utilizing biomimetics, thus examining and prototyping brain and central nervous system functions. Today,
many unsolved problems plague biosystems—from the baseline functionality of neurons to the capabilities
of neuronal aggregates, from information processing to information measures, from the phenomena utilized
xvii
to the cellular mechanisms exhibited, and so on. Even though significant challenges still exist, rapid progress
and new discoveries have been made in recent years on both fundamental and technological forefronts. This
progress and some of its major findings are covered in this handbook. The handbook consists of four sections,
providing coherence in its subject matter. The six chapters of Section I: Molecular and Nano Electronics: Device-
and System-Level are as follows:
r
Electrical Characterization of Self-Assembled Monolayers
r
Molecular Electronic Computing Architectures
r
Unimolecular Electronics: Results and Prospects
r
Carbon Derivatives
r

System-Level Design and Simulation of Nanomemories and Nanoprocessors
r
Three-Dimensional Molecular Electronics and Integrated Circuits for Signal and Information
Processing Platforms
These chapters report the device physics of molecular devices (
M
devices), the synthesis of those
M
devices,
the design of
M
ICs, and devising
M
PPs. Meaningful results on device- and system-level fundamentals are
offered, and envisioned technologies and engineering practices are documented.
Section II: Nanoscaled Electronics consists of the following six chapters:
r
Inorganic Nanowires in Electronics
r
Quantum Dots in Nanoelectronic Devices
r
Self Assembly of Nanostructures Using Nanoporous Alumina Templates
r
Neuromorphic Networks of Spiking Neurons
r
Allowing Electronics to Face the TSI Era—Molecular Electronics and Beyond
r
On Computing Nano-Architectures using unreliable Nanodevices or on Yield-Energy-Delay Logic
Designs
These chapters focus on nano- and nanoscaled electronics. Various practical solutions are reported.

Section III: Biomolecular Electronics and Processing covers recent innovative results in biomolecular elec-
tronics and memories. The six chapters included are
r
Properties of “G-Wire” DNA
r
Metalloprotein Electronics
r
Localization and Transport of Charge by Nonlinearity and Spatial Discreteness in Biomolecules
and Semiconductor Nanorings. Aharonov–Bohm Effect for Neutral Excitons
r
Protein-Based Optical Memories
r
Subneuronal Processing of Information by Solitary Waves and Stochastic Processes
r
Electronic and Ionic Conductivities of Microtubules and Actin Filaments, Their Consequences for
Cell Signaling and Applications to Bioelectronics
Each chapter is of practical importance regarding the envisioned biomolecular platforms, and will help in
comprehending significant phenomena in biosystems.
The eight chapters of Section IV: Molecular and Nano Electronics: Device-Level Modeling and Simulation
focus on various aspects of high-fidelity modeling, heterogeneous simulations, and data-intensive analysis.
The chapters included consist of the following:
xviii
r
Simulation Tools in Molecular Electronics
r
Theory of Current Rectification, Switching, and the Role of Defects in Molecular Electronic Devices
r
Complexities of the Molecular Conductance Problem
r
Nanoelectromechanical Oscillator as an Open Quantum System

r
Coherent Electron Transport in Molecular Contacts: A Case of Tractable Modeling
r
Pride, Prejudice, and Penury of ab initio Transport Calculations for Single Molecules
r
Molecular Electronics Devices
r
An Electric Cotunneling Model of STM-Induced Unimolecular Surface Reactions
These chapters provide the reader with valuable results that can be utilized in various applications, with a
major emphasis on the device-level fundamentals.
The handbook’s chapters report the individual authors’ results. Therefore, in reading different chapters,
the reader may observe some variations and inconsistencies in style, definitions, formulations, findings, and
vision. This, in my opinion, is not a weakness but rather a strength. In fact, the reader should be aware
of the differences in opinions, the distinct methods applied, the alternative technologies pursued, and the
various concepts emphasized. I truly enjoyed collaborating with all the authors and appreciate their valuable
contribution. It should be evident that the views, findings, recommendations, and conclusions documented in
the handbook’s chapters are those of the authors’, and do not necessarily reflect the editor’s opinion. However,
all the chapters in the book emphasize the need for further research and development in molecular and
nanoelectronics, which is today’s engineering, science, and technology frontier.
It should be emphasized that no matter how many times the material has been reviewed, and effort spent to
guarantee the highest quality, there is no guarantee this handbook is free from minor errors, and shortcomings.
If you find something you feel needs correcting, adjustment, clarification, and/or modification, please notify
me. Your help and assistance are greatly appreciated and deeply acknowledged.
Acknowledgments
Many people contributed to this book. First, I would like to express my sincere thanks and gratitude to all
the book’s contributors. It is with great pleasure that I acknowledge the help I received from many people
in preparing this handbook. The outstanding Taylor & Francis team, especially Nora Konopka (Acquisitions
Editor, Electrical Engineering), Jessica Vakili, and Amy Rodriguez (Project Editor), helped tremendously, and
assisted me by offering much valuable and deeply treasured feedback. Many thanks to all of you.
Sergey Edward Lyshevski

Department of Electrical Engineering
Rochester Institute of Technology
Rochester, NY, 14623-5603, USA
E-mail:
Web cite: www.rit.edu/∼seleee
xix

I
Molecular
and Nano
Electronics:
Device- and
System-Level
1 Electrical Characterization of Self-Assembled Monolayers
Wenyong Wang, Takhee Lee, Mark A. Reed 1-1
Introduction
•
Theoretical Background of Tunneling
•
Experimental
Methods
•
Electronic Conduction Mechanisms in Self-Assembled Alkanethiol
Monolayers
•
Inelastic Electron Tunneling Spectroscopy of Alkanethiol
Sams
•
Conclusion
2 Molecular Electronic Computing Architectures 2-1

Present Microelectronic Technology
•
Fundamental Physical Limitations of Present
Technology
•
Molecular Electronics
•
Computer Architectures Based on Molecular
Electronics
•
Characterization of Switches and Complex Molecular Devices
•
Conclusion
3 Unimolecular Electronics: Results and Prospects
Robert M. Metzger 3-1
Introduction
•
Donors and Acceptors; Homos and Lumos
•
Contacts
•
Two-Probe,
Three-Probe, and Four-Probe Electrical Measurements
•
Resistors
•
Rectifiers or
Diodes
•
Switches

•
Capacitors
•
Future Flash Memories
•
Field-Effect
Transistors
•
Negative Differential Resistance Devices
•
Coulomb Blockade Device
and Single-Electron Transistor
•
Future Unimolecular Amplifiers
•
Future Organic
Interconnects
•
Acknowledgments
4 Carbon Derivatives
Rikizo Hatakeyama 4-1
Introduction
•
Nanoelectronics – Oriented Carbon Fullerenes
•
Alignment-Controlled
Pristine Carbon Nanotubes Motivation Background
•
Nano-Electronic – Oriented Carbon
Nanotubes

•
Molecular Electronics Oriented Carbon Nanotubes
•
Summary and
Outlook
•
Acknowledgments
I-1
I
-2 Nano and Molecular Electronics Handbook
5 System-Level Design and Simulation of Nanomemories and Nanoprocessors
Shamik Das, Carl A. Picconatto, Garrett S. Rose, Matthew M. Ziegler,
James C. Ellenbogen 5-1
Introduction
•
Molecular Scale Devices in Device-Driven Nanocomputer
Design
•
Crossbar-Based Design for Nanomemory Systems
•
Beyond Nanomemories:
Design of Nanoprocessors Integrated on the Molecular Scale
•
Conclusion
6 Three-Dimensional Molecular Electronics and Integrated Circuits for
Signal and Information Processing Platforms
Sergey Edward Lyshevski 6-1
Introduction
•
Data and Signal Processing Platforms

•
Microelectronics and
Nanoelectronics: Retrospect and Prospect
•
Performance Estimates
•
Synthesis
Taxonomy in Design of
M
ICS and Processing Platforms
•
Bimolecular Processing and
Fluidic Molecular Electronics: Neurobiomimetics, Prototyping, and
Cognition
•
Biomolecules and Ion Transport: Communication Energetics
Estimates
•
Applied Information Theory and Information Estimates with Applications to
Biomolecular Processing and Communication
•
Fluidic Molecular
Platforms
•
Neuromorphological Reconfigurable Molecular Processing
Platforms
•
Towards Cognitive Information Processing Platforms
•
The Design of

Three-Dimensional Molecular Integrated Circuits: Data Structures, Decision Diagrams,
and Hypercells
•
Decision Diagrams and Logic Design of
M
ICS
•
Hypercell
Design
•
Three-Dimensional Molecular Signal/Data Processing and Memory
Platforms
•
Hierarchical Finite-State Machines and Their Use in Hardware and Software
Design
•
Adaptive Defect-Tolerant Molecular Presenting-and-Memory
Platforms
•
Hardware–Software Design
•
The Design and Synthesis of Molecular
Electronic Devices: Molecular Towards Molecular Integrated Circuits
•
Molecular
Integrated Circuits
•
Modeling and Analysis of Molecular Electronic Devices
•
Particle

Velocity
•
Particle and Potentials
•
The Schr
¨
odinger Equation
•
Quantum Mechanics
and Molecular Electronic Devices: Three-Dimensional Problems
•
Green’s Function
Formalism
•
Multiterminal Quantum-Effect
ME
Devices
•
Conclusions
1
Electrical
Characterization of
Self-Assembled
Monolayers
Wenyong Wang
Takhee Lee
Mark A. Reed
1.1 Introduction
1-2
1.2 Theoretical Background of Tunneling

1-3
Electron Tunneling
•
Inelastic Electron Tunneling
1.3 Experimental Methods
1-6
Self-Assembled Monolayers of Alkanethiols
•
Methods of
Molecular Transport Characterization
•
Device Fabrication
•
Lock-in Measurement for IETS Characterizations
1.4 Electronic Conduction Mechanisms in Self-Assembled
Alkanethiol Monolayers
1-12
Conduction Mechanisms of Metal-SAM-Metal Junctions
•
Previous Research on Alkanethiol SAMs
•
Sample
Preparation
•
Tunneling Characteristics of Alkanethiol SAMs
1.5 Inelastic Electron Tunneling Spectroscopy
of Alkanethiol SAMs
1-27
A Brief Review of IETS
•

Alkanethiol Vibrational Modes
•
IETS of Octanedithiol SAM
•
Spectra Linewidth Study
1.6 Conclusion 1-38
References
1-38
Abstract
Electrical characterization of alkanethiol self-assembled monolayers (SAMs) has been performed using
a nanometer-scale device structure. Temperature-variable current-voltage measurement is carried out to
distinguish between different conduction mechanisms and temperature-independent transport charac-
teristics are observed, revealing that tunneling is the dominant conduction mechanism of alkanethiols.
Electronic transport through alkanethiol SAMs is further investigated with the technique of inelastic elec-
trontunnelingspectroscopy(IETS).Theobtained IETSspectra exhibitcharacteristicvibrational signatures
of the alkane molecules used, presenting direct evidence of the presence of molecular species in the device
structure. Further investigation on the modulation broadening and thermal broadening of the spectral
peaks yields intrinsic linewidths of different vibrational modes, which may give insight into molecular
conformation and prove to be a powerful tool in future molecular transport characterization.
1-1
1
-2 Nano and Molecular Electronics Handbook
1.1 Introduction
The research field of nanoscale science and technology has made tremendous progress in the past decades,
ranging from the experimental manipulations of single atoms and single molecules to the synthesis and
possible applications of carbon nanotubes and semiconductornanowires [1–3]. As the enormous literature
has shown, nanometer scale device structures provide suitable testbeds for the investigations of novel
physics in a new regime, especially at the quantum level, such as single electron tunneling or quantum
confinement effect [4,5]. On the other hand, as the semiconductor device feature size keeps decreasing,
the traditional top-down microfabrications will soon enter the nanometer range, and further continuous

downscaling will become scientifically and economically challenging [6]. This will motivate researchers
around the world to find alternative ways to meet future increasing computing demands.
With a goal of examining individual molecules as self-contained functioning electronic components,
molecular transport characterization is an active part of the research field of nanotechnology [2,3]. In
1974, a theoretical model of a unimolecular rectifier was proposed, according to which a single molecule
consisting of an electron donor region and an electron acceptor region separated by a σ bridge would
behave as a unimolecular p-n junction [7]. However, an experimental realization of such a unimolecular
device was hampered by the difficulties of both the chemical synthesis of this type of molecule and the
microfabrication of reliable solid-state test structures. A publication in 1997 reported an observation of
such a unimolecular rectification in a device containing Langmuir–Blodgett (L-B) films; however, it is
not clear if the observed rectifying behavior had the same mechanism since it was just shown in a single
current-voltage [I(V)] measurement [8]. In the meantime, instead of using L-B films, others proposed to
exploit self-assembled conjugated oligomers as the active electronic components [9,10] and started the
electrical characterization of monolayers formed by the molecular self-assembly technique [2].
Molecular self-assembly is an experimental approach to spontaneously forming highly ordered mono-
layers on various substrate surfaces [11,12]. Earlier research in this area includes the pioneering study of
alkyl disulfide monolayers formed on gold surfaces [13]. This research field has grown enormously in the
past two decades and self-assembled monolayers (SAMs) have found their modern-day applications in
various areas, such as nanoelectronics, surface engineering, biosensoring, etc. [11].
Various test structures have been developed in order to carry out characterizations of self-assembled
molecules, and numerous reports have been published in the past several years on the transport char-
acteristics [2,3,14,15]. Nevertheless, many of them have drawn conclusions on transport mechanisms
without performing detailed temperature-dependent studies [14,15], and some of the molecular effects
were shown to be due to filamentary conduction in further investigations [16–21], highlighting the need
to institute reliable controls and methods to validate true molecular transport [22]. A related problem is
the characterization of molecules in the active device structure, including their configuration, bonding,
and even their very presence.
In this research work, we conduct electrical characterization of molecular assemblies that exhibit under-
stood classical transport behavior and can be used as a control for eliminating or understanding fabrication
variables. A molecular system whose structure and configuration are well-characterized such that it can

serve as a standard is the extensively studied alkanethiol [CH
3
(CH
2
)
n−1
SH] self-assembled monolayer
[11,22–25]. This system forms a single van der Waals crystal on the Au(111) surface [26] and presents a
simple classical metal–insulator–metal (MIM) tunnel junction when fabricated between metallic contacts
because of the large HOMO–LUMO gap (HOMO: highest occupied molecular orbital; LUMO: lowest
unoccupied molecular orbital) of approximately 8 eV [27]. Utilizing a nanometer scale device structure
that incorporates alkanethiol SAMs, we demonstrate devices that allow temperature-dependent I(V)
[I(V,T)] and structure-dependent measurements [24]. The obtained characteristics are further compared
with calculations fromacceptedtheoretical models of MIMtunneling, andimportant transportparameters
are derived [24,28].
Electronic transport through alkanethiol SAM is further investigated with the technique of inelastic
electron tunneling spectroscopy (IETS) [25,29]. IETS was developed in the 1960s as a powerful spec-
troscopic tool to study the vibrational spectra of organic molecules confined inside metal–oxide–metal